Characterisation of cobalt‐binding proteins in occupational cobalt exposuret†

In animal experimentations cobalt is found to be carcinogenic under conditions which are comparable with a possible exposure of human beings at the workplace.^1,2 Little is known about binding and distribution of incorporated cobalt in blood.

Blood, serum and plasma of workers occupationally exposed to cobalt were analyzed concerning cobalt‐binding. The samples were focused by preparative IEF in layers of granulated gels. The cobalt concentrations in the isolated fractions were measured with the aid of flameless atomic absorption spectrometry. The whole blood samples exhibit peaks with different sizes in the pH‐5‐ and ‐7‐range. The proportion of these peaks can change with individual samples. In serum and plasma cobalt is found only in the pH‐5‐range.

When separated by gelelectrophoresis under denaturating conditions the cobalt‐fractions in all blood, serum and plasma samples shows a similar protein pattern. Several proteins with different molecular weights are detected in the pH‐5‐fractions, whereas only hemoglobin is found in the pH‐7‐fractions. In agreement with these results is the refocusing in ultrathin‐layer of polyacrylamide. Heterogeneous protein patterns are demonstrated with the pH‐5‐fractions; the pH‐7‐fractions yield only the hemoglobin pattern.

In vivo cobalt is bound to plasma proteins‐perhaps‐albumin^3,4‐and hemoglobin. Till now the chemical structure of the binding is unknown.     

Online solid phase preconcentration using EGDMA–MAA copolymer for lead determination by FAAS

A Ethylene glycol dimethacrylate (EGDMA) methacrylic acid (MAA) resin was used for preconcentration of lead at trace levels in water samples. For this purpose, a flow-injection, solid phase extraction method was developed for the determination of lead by flame atomic absorption spectrometry. Lead ions were sorbed on a EGDMA–MAA column at pH 4, followed by an elution step using 288 µL of 4.0 M nitric acid solution and determination by flame atomic absorption spectrometry. Optimum conditions for quantitative sorption involving the pH, sample volume, loading and elution flow rates, eluent type, and volume were investigated. A 868-fold enrichment factor could be reached. The detection limit for the water samples, estimated from the noise on the signal obtained for 250 mL of 10 µg L^?1 loaded at 4.9 mL min^?1 was 1.04 µg L^?1. The method was applied for lead determination in river water samples collected in Edirne, Turkey. Recoveries of spiked solutions (10 µg L^?1) to river water samples were quantitative. Finally, the method was validated by the analysis of certified reference material SRM 2704 (Buffalo River Sediment).     

麦饭石对Pb2+离子吸附的动力学研究

本文研究了水溶液中麦饭石对Ｐｂ＾２＋离子去除的反应动力学,考察了ＭＦＳ粒度、溶液ＰＨ值和铅离子的初始浓度对吸附反应的影响。结果表明,ＭＦＳ对Ｐｂ＾２离子具有较强的吸附性能,ＰＨ值是影响吸附的主要因素,Ｐｂ＾２＋离子吸附的最初速率与浓度符合一级反应动力学;吸附过程符合Ｌａｎｇｍｕｉｒ吸附等温式;离子交换和表面络合反应是主要吸附形式。     

Influence of some abiotic environmental factors on acute toxicity of inorganic lead to Cyprinus carpio var communis (Linn.) and Catla catla (Ham.) in simulated toxic aquatic environment

With the increase of water hardness from 60 to 720?mg/L CaCO₃, total alkalinity from 32 to 376?mg/L CaCO_3, pH from 7.6 to 7.9 and chloride from 28 to 350?mg/L, 96?h LC₅₀ on the basis of total lead increased from 8.2 to 1291?mg/L for Cyprinus carpio and 5.3 to 865?mg/L for Catla catla, when soil sediments were included these values were further raised to 1356 and 874?mg/L, respectively. The dissolved lead LC₅₀ values in all the treatments of soil and water was consistent with fixed amount of dissolved lead (1.04–1.78?mg/L) being needed for median lethal toxicity. Total lead toxicity also decreased with increase in pH from 6.3 to 11.3. 96?h LC₅₀ values increased for common carp 15 to 631?mg/L and for catla, 8 to 355?mg/L. But dissolved lead toxicity was found to increase with the increase of pH from 6.3 to 11.3 for both common carp (LC₅₀, 3.53 to 0.24?mg/L) and catla (LC₅₀, 2.21 to 0.09?mg/L). Removal of dissolved Pb with increasing carbonate content, particulate matter and pH due to adsorption, precipitation or coprecipitation reaction, reduced the dissolved lead concentration and thus the total lead toxicity. Increase in toxicity of lead with increase of exposure time was the biological response of longer contact time and decrease in dissolved lead toxicity with decrease in pH was due to increase H⁺ ion competition.     

Solid phase extraction of trace metals from environmental samples using Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone and determination by inductively coupled plasma–atomic emission spectrometry

A method for the solid phase extraction of trace metals, namely Co, Cu, Pb, Ni and Zn, from environmental and biological samples using column Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone (HPPPTSC) and determination by inductively coupled spectrometry (ICP–AES) has been developed. The reagent has the capacity to form chelate complexes with the metals because of three binding sites in the reagent molecule. The optimum experimental conditions for the quantitative sorption of five metals, pH, effect of flow rate, concentration of eluent, sorption capacity and the effect of diverse ions on the preconcentration of analytes have been investigated. The sorption capacity of the resin has 83, 127, 35, 88 and 85?µmol?g^?1 for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺, respectively. The preconcentration factors for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺ were 100, 110, 120, 140 and 150, respectively. The accuracy of the proposed procedure was evaluated by standard reference materials. The achieved results were in good agreement with certified values. The proposed method was applied for the determination of trace metals in river water and plant leaves.     

环境样品中痕量铅的流动注射在线分离及分光光度检测

1　IntroductionLeadiswellknownasoneofthemosttoxicmetalsandnotedinthefieldofenvironmentalchemistry[1 ] .Theleadconcentrationinnaturalwaterisextremelylow (sub μg·l-1 level)sothatsomepreconcentrationstepmustbeincludedtoassurethesensitivityofaconventionalin…     

Electro-remediation of tailings from a multi-metal sulphide mine: comparing removal efficiencies of Pb,Zn, Cu and Cd

Sulphidic mine tailings characterised by high concentrations of heavy metals (Pb 3532?±?97?mg/kg, Zn 8450?±?154?mg/kg, Cu 239?±?18?mg/kg and Cd 14.1?±?0.3?mg/kg) and abundant carbonate (17%) were subjected to eight lab-scale electrodialytic remediation (EDR) experiments to investigate the influence of current density, treatment time and particle size on removal efficiency. Pb and Cu removal improved when increasing current density, while Zn and Cd removal did not. In contrast Zn and Cd removal improved by grinding the tailings, while Pb and Cu removal did not. At the highest current density (1.2?mA/cm²), 94%, 75%, 71% and 67% removal of Pb, Zn, Cu and Cd could be achieved, respectively, on grinded tailings in 28 days. Sequential chemical extraction made before and after EDR revealed larger oxidisable fractions of Zn, Cu and Cd, representing large fractions of sulphides, which was likely to be the main barrier to be removed as efficiently as Pb. This was in accordance with acid/base extraction tests in which Pb showed high solubility at both high and low pH (up to 65% and 86% of extraction, respectively), while considerable extraction of Zn (55%) happened only at low pH; and very limited extraction (<20%) of Cu and Cd occurred at any pH.     

Effects of dietary copper exposure on accumulation,growth, and hematological parameters in Cyprinus carpio

The influence of dietary copper (Cu) exposure on accumulation, growth, and hematological parameters was investigated in Cyprinus carpio after sub-chronic ingestion of 0, 250, 500, 750 or 1000?mg?kg^?1 for 60 days. The profile of Cu accumulation among tissues in C. carpio was dependent on the exposure period and Cu concentration. Liver of C. carpio was the predominant storage tissue and the order of Cu accumulation in tissues was liver?>?intestine?> gill?>?kidney?>?muscle. Cu concentration at >125?mg?kg^?1 reduced growth rate, and was inversely related to growth. The RNA?:?DNA ratios were not affected by exposure and there was no correlation between growth rate and RNA?:?DNA ratio in liver and muscle. There were no significant effects of exposure on blood parameters except for magnesium. Cu exposure time and dose increased the serum glutamic-oxaloacetic transaminase (SGOT) and serum glutamic-pyruvic transaminase (SGPT) activity levels.     

A comparative study of modified and unmodified maize tassels for removal of selected trace metals in contaminated water

Powdered maize tassels were studied and found to exhibit metal sorption properties due to the availability of functional groups. The tassels have a high amount of soluble organic substances that can dissolve in aqueous media, contributing to secondary pollution during a water treatment process. A chelating agent was chemically attached on the maize tassels with a view to increase the sorption capacity, minimize leaching, and enhance the tassels’ stability. Thermogravimetric analysis confirmed that modification improved their thermal stability to withstand temperatures above 600°C as well as reduced the “secondary pollution”. The modified sorbent was employed for the sorption of lead, copper, and cadmium ions in both the model solutions and the real samples. The contact time and pH were optimized after which Langmuir and Freundlich isotherms were applied to the data. The sorption capacities for Cu²⁺, Cd²⁺, and Pb²⁺ improved from 3.4, 0.8, and 1.7?g?kg^?1, respectively, to 6.3, 2.6, and 2.6?g?kg^?1 in the same order. The sorbent was shown to remove up to 95% of the metals in less than 10 min. This study has a potential application for the remediation of polluted waters.     

Modelling the kinetics and equilibrium properties of cadmium biosorption by river green alga and water hyacinth weed

Cadmium biosorption properties of non-living, dried river green alga from a river source, and water hyacinth weed, Eichhornia crassipes from a lake in Zimbabwe have been investigated. The cadmium uptake was found to depend on initial pH, uptake being apparently minimal at low pH values and increasing with an increase in pH. Cadmium biosorption kinetics by both samples is fast, with 80% of total uptake occurring within 60?min. The effect of initial solution pH and initial cadmium concentration on cadmium biosorption from a cadmium solution has been studied. The data for algal biomass fitted the Langmuir monolayer adsorption isotherm, while the biosorption of the metal by water hyacinth weed fitted the Freundlich adsorption isotherm with 1/n values all less than 1. Maximum metal uptake capacities were recorded using 0.35?g of biomass and a 250?mg?L^?1 cadmium solution at pH 6.5 and at 25°C and these were about 85 and 50?mg?L^?1 for water hyacinth weed and green alga, respectively, showing that water hyacinth weed offered a greater potential for cadmium uptake. The absorption was described by pseudo-second order rate model and the rate constant and equilibrium sorption capacity are reported.     

Preconcentration of some trace metal ions on coated alumina modified by 1-((6-(-(2-hydroxynaphthalen-1-yl)methyleneamino) hexylimino) methyl) naphthalen-2-ol

A sensitive and efficient method for preconcentration of trace amounts of some metal ions such as Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Pb²⁺, Cd²⁺, Cr³⁺, and Fe³⁺ ions based on modification of sodium-dodecyl-sulphate (SDS) coated alumina with 1-(6-(-(2-hydroxynaphthalen-1-yl) methyleneamino) hexylimino) methyl) naphthalen-2-ol (HNMAHN) is reported. The method is based on the uptake of these ions following their chelation with HNMAHN and their recovery using a suitable eluent. The influence of parameters such as pH, concentration of ligand and amount of coated alumina, SDS concentration, eluent (type and concentrations), and elution volume on metal ion recoveries are investigated. The preconcentration factor is 150 (10?mL elution volume) for a 1500?mL sample volume. The method has been successfully applied for extraction and determination of these ions content in some real samples. Extraction efficiency is generally >95% with low relative standard deviations between 1.8% and 2.4 %.     

Toxic responses of different organs following occupational exposure to sub-threshold limit value levels of paving asphalt fumes

The main purpose of this study was to ascertain whether occupational exposure to asphalt fumes, under normal working conditions, is associated with any hepatotoxic, nephrotoxic, or hematotoxic response. This was a cross-sectional study in which 210 subjects (80 exposed and 130 reference subjects) were investigated. Using standard methods, atmospheric concentrations of total particulate and benzene-soluble fractions of asphalt fumes were measured. Additionally, urine and blood samples were taken from subjects for complete blood count, white blood cell differential test, urinalysis, and routine biochemical tests of kidney and liver function. Both groups were similar as far as their demographic variables and smoking habits were concerned. The levels of exposure to total particulate and benzene-soluble fractions were estimated to be 0.9?±?0.2 and 0.32?±?0.09 mg m^?3, respectively (mean?±?SD), both of which being lower than the existing threshold limit values. Statistically, significant associations between exposure to asphalt fumes and changes in most liver and kidney function tests and complete blood count parameters provided circumstantial evidence in favor of the notion that exposure to sub-threshold limit value levels of total particulate and benzene-soluble fractions is associated with early liver and kidney dysfunction as well as hematological disorders.     

Carbon paste electrode modified with chromium thiopental for the potentiometric flow injection analysis of chromium (III)

A chemically modified carbon paste electrode for chromium (III) based on the formation of ion-association complex of chromium with 5-ethyl-6-oxo-5-pentan-2-yl-sulfanyl-pyrimidin-4-olate (thiopental, THP) as electroactive ion-exchanger (Cr-THP) was prepared and investigated. The electrode has a linear dynamic range of 1.7?×?10^?6–1.3?×?10^?2?mol?L^?1, with a Nernstian slope of 19.6?±?0.5?mV per decade and a detection limit of 9.0?×?10^?7?mol?L^?1. It has a fast response time of <15?s and can be used for at least 7 weeks without any considerable divergence in potential. The proposed sensor revealed good selectivity for Cr(III) over a wide variety of mono-, di-, and trivalent cations and could be used in the pH range of 2.3–6.5. The proposed electrode was used in batch measurements and in flow injection analysis. The Cr-CMCPE was successfully applied for the determination of Cr(III) in real samples (wastewater of hot dip galvanizing unit and alloys). The present electrode was also used as an indicator electrode in potentiometric titration of Cr(III). The results were highly satisfactory.     

Decomposition of perfluorooctanoic acid by microwaveactivated persulfate: Effects of temperature, pH, and chloride ions

Microwave-hydrothermal treatment of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water with persulfate (S₂O ₈ ^2? ) has been found effective. However, applications of this process to effectively remediate PFOA pollution require a better understanding on free-radical scavenging reactions that also take place. The objectives of this study were to investigate the effects of pH (pH = 2.5, 6.6, 8.8, and 10.5), chloride concentrations (0.01?C0.15 mol·L^?1), and temperature (60°C, 90°C, and 130°C) on persulfate oxidation of PFOA under microwave irradiation. Maximum PFOA degradation occurred at pH 2.5, while little or no degradation at pH 10.5. Lowering system pH resulted in an increase in PFOA degradation rate. Both high pH and chloride concentrations would result in more scavenging of sulfate free radicals and slow down PFOA degradation. When chloride concentrations were less than 0.04 mol·L^?1 at 90°C and 0.06 mol·L^?1 at 60°C, presence of chloride ions had insignificant impacts on PFOA degradation. However, beyond these concentration levels, PFOA degradation rates reduced significantly with an increase in chloride concentrations, especially under the higher temperature.     

Blood lead level in the children of western Uttar Pradesh,India

The objective of this study was to determine the blood lead levels (blls) of children under an age of 5 years living in western Uttar Pradesh, India. A total of 100 blood samples, 100 drinking water samples, and 21 vegetable samples were assessed for lead contamination. Blood levels in the range of 30–116?µg?L^?1 were observed at Kazipur village. The levels of lead in water samples were reported to be in the range of 0.006–0.095?ppm and identified at up to 9.5 times the stated permissible limit. A significant positive correlation (+0.679) was obtained between blls and water lead levels. All vegetable samples were also contaminated with lead up to 12 times higher than the permissible limit of 2.5?mg?kg^?1 of Prevention of Food Adulteration Act (PFA) 1954. The cottage lead battery industry, industrial effluents, and lead paints were identified as possible factors for lead incidence in the study area. Lead may be associated with increased antisocial activities of the children living in western Uttar Pradesh. Children with elevated blls had poorer nutritional status than those with normal levels, and parents did not know that lead causes health problems. A national population-based study is recommended to determine the prevalence of elevated blls.     

Selective separation and preconcentration studies of chromium(VI) with Alamine 336 supported liquid membrane

Chromium compounds have received considerable attention because these are used extensively in such industrial applications as electroplating, steelmaking, tanning of leather goods, and corrosion inhibition. The use of supported liquid membranes (SLMs) to remove metals from wastewaters has actively been pursued by the scientific and industrial community. In the present work, the selective separation and preconcentration of Cr(VI) ions has been studied by using a commercial amine as the membrane liquid on the porous polypropylene support. Permeation experiments were conducted on a laboratory scale batch reactor made up of perspex, with a memberane fixed amid the two chambers. The flux of Cr(VI) ions was found to be maximum (3.15?×?10^?5?mol?cm^?2?s^?1) around pH 1. Above and below this pH the flux decreases. Distribution studies show that an increase in the amine concentration leads to higher distribution coefficients at fixed pH values. At pH around unity, the distribution of Cr(VI) ions into the organic phase was found to be maximum, of the order of 56.3. The Cr(VI) transport through the membrane increases with rise in temperature. In order to check the long-term efficiency of the flat sheet SLM, an experiment was conducted with higher Cr(VI) concentration (5000?ppm) for 24?h, at optimised parameters. It was observed that in 24?h, about 1/5th of the feed Cr(VI) is left over while the rest is transported. However, minute organic droplets were also seen in the feed and strip compartments, after 1 day. This observation suggested the loss of membrane liquid. The feasibility of preconcentration of Cr(VI) by using the proposed SLM parameters, was also studied by using the hollow fibre (HF) system. Highest enrichment factor (E.F) value was obtained for 50?mg?L^?1 whereby all of the metal was transported to the stripping phase and the resulting Cr concentration was 688?mg?L^?1 (E.F?=?13.8). It was observed that while treating more diluted solutions, the enrichment factor decreases. The values of E.F equal to 8.9 and 11.3 were found for initial Cr concentration of 10 and 30?mg?L^?1.     

Immunoprotective effect of curcumin on cypermethrin-induced toxicity in rats

Immunotoxicological effects of cypermethrin and their reversal by curcumin following oral administration were evaluated in rats. Mature male Wistar rats were orally administered cypermethrin (25?mg?kg^?1 body wt), curcumin (100?mg?kg^?1 body wt) or both daily for 4 weeks. At the end of fourth week, hematological, serum biochemical, and immunological parameters were studied. Subchronic exposure to cypermethrin significantly reduced body weight, total leukocyte count, lymphocyte count, serum total protein, serum albumin, serum globulin, antibody titer against sheep red blood cells, and cell-mediated immunity. Concomitant curcumin administration restored the changes in the body weight, hematological parameters, and serum biochemical indices and significantly increased the antibody titer, and cell mediated immunity. These results suggest that concurrent curcumin treatment has a beneficial role in mitigating immunotoxicological and other adverse effects of cypermethrin.     

Risk assessment of children's blood lead level in some rural habitations of western Uttar Pradesh,India

The objective of this study was to determine the blood lead level (BLL) of children aged under 5 living in western Uttar Pradesh, India. A total of 100 blood samples, 100 drinking water samples, and 21 vegetable samples were assessed for lead (Pb) contamination. BLL was observed in the range of 3–11.58?µg?dL^?1 with a maximal level of 11.58?±?0.05?µg?dL^?1 in Kazipur village. Lead in water samples was detected in the range of 0.006–0.095?ppm and identified at upto 9.5-fold higher than the stated permissible limit. A significant positive correlation (+0.679) was obtained between BLL and water Pb levels. All vegetable samples were also contaminated with Pb upto 12-fold higher than the permissible limit of 2.5?µg?g^?1 of Prevention of Food Adulteration Act (PFA) 1954. Untreated industrial effluents were identified as the responsible factors for Pb occurrence in the study area. The presence of lead may be associated with the increased antisocial activities of children living in western Uttar Pradesh. Children with elevated BLL had poorer nutritional status than those with background Pb levels. There is an urgent need for a national campaign to monitor the BLL of children in India.     

Lead-induced alterations in protein-deficient rat liver–role of zinc

This study was designed to determine the protective effects of zinc (Zn) using liver marker enzymes in the serum and liver along with hepatic elemental profile in lead (Pb)-treated protein-deficient (PD) Sprague–Dawley male rats. Zn in the form of zinc sulfate at a dose of 227?mg?L^?1 in drinking water was administrated to control, PD as well as Pb-treated PD rats for 8 weeks. Pb treatment was given orally as lead acetate at a dose level of 100?mg?kg^?1 body weight to control and PD rats. The effects of different treatments were studied on the activities of enzymes that included alkaline phosphatase (ALP), aspartate aminotransferase (AST) and alanine aminotransferase (ALT) in serum. The status of different elements (Cl, K, Mn, Fe, Cu, Zn, Se, Rb, Pb) in liver was also studied. Rats given PD diet and Pb showed significant inhibition in serum ALP activity associated with significant elevation in both AST and ALT activities. Serum ALP activity showed a significant inhibition week 1 until week 8 in Pb-treated PD rats. In contrast, serum AST activity was elevated both at 3 and 8 weeks while serum ALT activity was elevated at 8 weeks in Pb-treated PD rats. Pb treatment to PD rats elevated hepatic ALP, AST and ALT activities but depressed hepatic AST. Zn supplementation to Pb-treated PD rats restored the altered enzyme activities. The levels of K, Fe, Cu, Zn, Se and Rb were altered in protein deficiency. Furthermore, treatment with Pb to these animals depressed the Cu levels. Zn treatment to Pb-treated PD animals tended to restore the levels of altered elements. Hence, the present study clearly suggests that Zn plays an important role in regulating the liver marker enzymes and essential elements under conditions of Pb toxicity and protein deficiency.